Multi-layer surface film

Abstract

A surface film is provided that includes a plurality of layers. The layers include a first clear coat layer made of a crosslinked polyurethane that is a reaction product of a reactive mixture that includes an isocyanate and a polyol that contains styrene repeat units and hydroxyl-containing (meth)acrylate repeat units. The surface film further includes a bulk layer made of a thermoplastic polyurethane and an adhesive layer. Optionally, the surface film includes a second clear coat layer that can be made of a polyurethane that is at least partially crosslinked. The resulting surface film can exhibit high stain resistance, high peel strength, excellent scratch resistance and self-healing properties.

Description

[Technical field]

[0001] Surfacing films for paint protection or paint replacement applications are provided. The provided films can be useful in paint protection or paint replacement applications, for example, for automotive and aerospace exteriors. [Background technology]

[0002] Surface films are applied to exterior surfaces to protect the underlying substrate from damage caused by environmental weathering, chemical exposure, heat, and / or abrasion. These films can be used to protect either painted or unpainted surfaces. When applied to painted surfaces, they are commonly referred to as paint protection films. When applied to unpainted surfaces, they can be used to provide color, in which case they can be referred to as body color films or paint replacement films.

[0003] Films made from polyurethanes can withstand harsh environments and are well suited for these applications. Polyurethanes are synthetic polymers of great commercial and industrial importance. They are generally prepared by reacting a polyfunctional isocyanate with a polyfunctional diol or polyol in the presence of a catalyst to produce a polymer containing carbamate (-NH-CO-O-) bonds. Thermoplastic polyurethanes are characterized by linear polymer chains with a self-arranged block structure, whereas thermoset polyurethanes are highly crosslinked by covalent bonds.

[0004] Depending on the components used to make the polyurethanes, these materials can be engineered to exhibit a high degree of chemical resistance and a wide range of material properties. Polyurethanes can also be very durable and flexible, making them desirable materials for many applications. Other useful commercial and industrial applications include high resilience foam sheets, rigid foam insulation panels, microcellular foam seals and gaskets, hoses, elastomeric wheels and tires, automotive suspension bushings, electrical potting compounds, high performance adhesives, coatings and sealants, synthetic fibers, and carpet underlay. Summary of the Invention

[0005] Conventional surface films exhibit varying degrees of scratch resistance, self-healing properties, and stain resistance, but there is still room for improvement. For example, there is still potential to improve both the initial adhesive peel strength and the aged adhesive peel strength. Furthermore, these products may have a strong odor as a result of residual solvents and / or other volatile compounds in the adhesive, which may provide an undesirable user experience. The scratch resistance and self-healing properties of these conventional films may also be limited by their composition and crosslink density.

[0006] The provided process and article uses copolymerized acrylic-styrene polyols containing multiple hydroxyl groups, which can dramatically increase the crosslink density compared to that of conventional film compositions. Furthermore, a dual-layer clearcoat layer structure can be used to reduce or eliminate the odor problem mentioned above.

[0007] In an exemplary process, the surface film can be produced by coating a first layer of a crosslinkable reactive polyurethane clear coat on a peelable polyester carrier web that is cured to produce a first clear coat layer, and then coating a second crosslinkable polyurethane clear coat layer on top of the first clear coat layer that is at least partially cured to provide a primer layer. One or more thermoplastic polyurethane layers can then be laminated to the exposed surface of the second clear coat layer of the crosslinkable polyurethane layer by an extrusion process or a thermal lamination process. The remaining surface of the thermoplastic polyurethane layer can then be laminated to a transfer adhesive.

[0008] The obtained surface film shows surprisingly high stain resistance and high initial adhesive peel strength and aged peel strength. The provided surface film can also show excellent scratch resistance and self-repairing properties. Also, when the above clear coat composition is incorporated into a two-layer structure, it can also substantially avoid the solvent odor caused by the adhesive. The process of producing the multi-layer coating film also allows significantly improved throughput yield and reduced factory cost.

[0009] In a first aspect, a surfacing film is provided, the surfacing film comprising a plurality of layers, in the following order: a first clearcoat layer comprising a crosslinked polyurethane that is the reaction product of a reactive mixture comprising an isocyanate and a polyol containing styrene repeat units and hydroxyl-containing (meth)acrylate repeat units, a bulk layer comprising a thermoplastic polyurethane, and an adhesive layer.

[0010] In a second aspect, there is provided a process for making a surfacing film, the process comprising disposing a first curable polyurethane clearcoat composition on a first release liner, the first curable polyurethane clearcoat composition comprising a copolymer of styrene and a hydroxyl-containing (meth)acrylate, only partially curing the first curable polyurethane clearcoat composition to provide a first clearcoat layer, disposing a second curable polyurethane clearcoat composition on the first clearcoat layer, at least partially curing the second curable polyurethane clearcoat composition to provide a second clearcoat layer on the first clearcoat layer, disposing a thermoplastic polyurethane layer on the second clearcoat layer, and disposing an adhesive layer on the thermoplastic polyurethane layer. [Brief description of the drawings]

[0011] [Figure 1] 1A-1C are side cross-sectional views of a surface film according to two exemplary embodiments. [Diagram 2] 1A-1C are side cross-sectional views of a surface film according to two exemplary embodiments. [Diagram 3] FIG. 2 is a block diagram illustrating an exemplary process for manufacturing a surface film.

[0012] Repeat use of reference characters in the specification and drawings is intended to represent the same or similar features or elements of the present disclosure. It is to be understood that those skilled in the art can devise numerous other modifications and embodiments that are within the scope and spirit of the principles of the present disclosure. The figures may not be drawn to scale. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] definition As used herein, "ambient conditions" means a temperature of 21 degrees Celsius and a pressure of 1 atmosphere (approximately 100 kilopascals); "Catalyst" means a substance that can increase the rate of a chemical reaction; "Diol" means a compound having exactly two hydroxyl functional groups; "Diisocyanate" means a compound containing exactly two isocyanate functional groups; "Cure" means to change the physical and / or chemical state of a composition, such as from a fluid to a less flowable state, from a viscous to a non-viscous state, from a soluble to an insoluble state, to reduce the amount of polymerizable material by consumption in a chemical reaction, or from a particular molecular weight material to a higher molecular weight; "Curable" means capable of being cured; "Fully cured" means that the composition has cured to a condition suitable for use in its intended application, such as percent conversion as determined by Fourier transform infrared spectroscopy (FTIR) using the method described in Chai, C, Hou, J, Yang, X, Ge, Z, Huang, M & Li, G 2018, 'Two-component waterborne polyurethane: Curing process study using dynamic in situ IR spectroscopy', Polymer Testing, vol. 69, pp. 259-265. "Partially cured" means cured to a state less than completely cured; "Polyisocyanate" means a compound having two or more isocyanate functional groups; "Polyol" means a compound having two or more hydroxyl functional groups. "Primary isocyanate" means that the carbon atom to which the isocyanate group is attached also has two hydrogen atoms. "Weight average molecular weight" refers to the weight average molecular weight by gel permeation chromatography (ie, size exclusion chromatography) using techniques known to those of skill in the art.

[0014] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As used herein, the terms "preferred" and "preferably" refer to embodiments described herein that may provide certain advantages, under particular circumstances, although other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and other embodiments are not excluded from the scope of the invention.

[0015] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an element followed by "a" or "the" may include one or more of the element and equivalents thereof known to those skilled in the art. Furthermore, the term "and / or" refers to one or all of the listed elements or a combination of any two or more of the listed elements.

[0016] It should be noted that the terms "comprises" and variations thereof do not have a limiting meaning when these terms appear in the accompanying description. Furthermore, "a," "an," "the," "at least one," and "one or more" are used interchangeably herein.

[0017] Relative terms such as left, right, front, rear, top, bottom, side, above, below, horizontal, vertical, etc. may be used herein, where the term is from the perspective seen in a particular view. However, these terms are used merely for ease of description and in no way limit the scope of the invention. The figures are not necessarily drawn to scale.

[0018] Throughout this specification, reference to "one embodiment," "a particular embodiment," "one or more embodiments," or "an embodiment" means that a particular feature, structure, material, or characteristic described with respect to that embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrases "in one or more embodiments," "in a particular embodiment," "in one embodiment," or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0019] Layer composition A multi-layer surfacing film according to one embodiment is shown in Figure 1 and designated herein by reference numeral 100. As shown, the surfacing film 100 includes a composite clear coat layer 102 that includes a first clear coat layer 104 and a second clear coat layer 106.

[0020] As shown, the first clear coat layer 104 has a top surface 108 and a bottom surface 110. The top surface 108, as shown, is optionally the exposed major surface of the surface film 100, but may optionally be covered by a protective liner or cover layer to avoid scratching the surface film 100 during storage and handling.

[0021] The first clearcoat layer 104 is a reaction product obtained by curing a reactive mixture. The reactive mixture includes monomeric compounds that react with each other to provide a cured cured layer. A preferred reactive mixture used to obtain the first clearcoat layer 104 is a reactive urethane composition including an isocyanate and a polyol containing styrene repeat units and hydroxyl-containing (meth)acrylate repeat units. In a preferred embodiment, the polyol is a copolymer including at least styrene repeat units and hydroxyl-containing (meth)acrylate repeat units. The copolymer may be a random copolymer, a block copolymer, or a combination thereof (e.g., a tapered block copolymer).

[0022] Useful copolymers have the following Structure I, which shows a copolymer of a hydroxyalkyl acrylate, styrene, and an alkyl (meth)acrylate: [ka] where R1 is a divalent alkylene group having 1 to 12 carbon atoms, R2 and R3 are independently either a hydrogen atom or a CH3 group, and R4 is an alkyl group having 1 to 8 carbon atoms.

[0023] In some embodiments, the hydroxyl-containing (meth)acrylate is a hydroxyalkyl (meth)acrylate. The hydroxyalkyl (meth)acrylate used in the polyol does not need to be particularly limited, and can include, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 2-hydroxyoctyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, or a combination thereof.

[0024] Having a functionality significantly greater than two to increase the hardness of the first clearcoat layer 104 can be an important technical advantage for polyols, such as the polyol of structure I above. The functionality of the polyol can be 2-50, 5-50, 10-50, or in some embodiments less than, equal to, or greater than 2, 3, 4, 5, 7, 10, 12, 15, 20, 25, 30, 35, 40, 45, or 50. The polyol can have a weight average molecular weight that is less than, equal to, or greater than 250 g / mol to 30,000 g / mol, 275 g / mol to 20,000 g / mol, 300 g / mol to 10,000 g / mol, or in some embodiments, 250 g / mol, 275, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 2000, 5000, 7000, 10,000, 15,000, 20,000, 25,000, or 30,000 g / mol.

[0025] The third monomer in structure I above need not be present, but may be a relatively high T monomer such as methyl methacrylate. g The incorporation of repeating monomer units improves the T g It may be beneficial to increase the viscosity of the polyol and improve the miscibility of this polyol with other polyols in the reactive mixture. Additional (meth)acrylate monomers may also be included to optimize the mechanical properties of the first clearcoat layer 104, if desired.

[0026] The reactive mixture used to produce the first clearcoat layer 104 can further include any number of additional polyols, including diols and polyols with more than two hydroxyl functional groups. Suitable polyols can include caprolactone polyols, polycarbonate polyols, polyester polyols, polyacrylate polyols, polyether polyols, polyolefin polyols, and mixtures thereof. The addition of these additional polyols can affect the T of the first clearcoat layer 104. gand can be beneficial in adjusting the overall mechanical properties. The additional polyol can represent 20 weight percent to 80 weight percent of the total weight of the reactive mixture used to produce the first clearcoat layer 104, or in some embodiments, less than, equal to, or greater than 20 weight percent, 22, 25, 27, 30, 32, 35, 37, 40, 42, 45, 46, 50, 55, 57, 60, 62, 65, 67, 70, 72, 75, 77, or 80 weight percent.

[0027] Overall, the polyol component used in producing the first clearcoat layer 104 may comprise less than, equal to, or greater than 25% by weight to 80% by weight, 30% by weight to 70% by weight, 30% by weight to 60% by weight, or in some embodiments, 25%, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80% by weight, based on the total weight of the uncured polyurethane composition.

[0028] Suitable isocyanates include diisocyanates and polyisocyanates with more than two isocyanate functional groups. In an exemplary embodiment, the polyisocyanate is a primary polyisocyanate, such as a primary aliphatic polyisocyanate. Primary polyisocyanates with three or more isocyanate functional groups can be made from primary diisocyanates, such as 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, or 1,4-cyclohexanedimethylene diisocyanate.

[0029] The polyisocyanate can represent 30% to 90% by weight, 40% to 80% by weight, 50% to 70% by weight, or in some embodiments a weight percentage less than, equal to, or greater than 30%, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by weight, based on the total weight of the uncured polyurethane composition.

[0030] The curable composition may further comprise a catalyst for promoting the reaction of the polyisocyanate with the polyol component. Catalysts useful for the polymerization of polyurethane include aluminum, bismuth, tin, vanadium, zinc, mercury, and zirconium-based catalysts, amine catalysts, and mixtures thereof. Preferred catalysts include tin-based catalysts such as dibutyltin compounds. Particularly preferred are catalysts selected from the group consisting of dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dimercaptide, dibutyltin dioctoate, dibutyltin dimaleate, dibutyltin acetonylacetonate, and dibutyltin oxide.

[0031] Suitable amounts of catalyst can be from 0.001% to 0.2%, from 0.001% to 0.15%, from 0.001% to 0.1% by weight, or in some embodiments can be less than, equal to, or greater than 0.001%, 0.002, 0.005, 0.007, 0.01, 0.02, 0.05, 0.07, 0.1, 0.12, 0.15, 0.17, or 0.2% by weight based on the total weight of the uncured polyurethane composition.

[0032] If desired, other ingredients such as ultraviolet light absorbers, hindered amines, leveling agents, colorants, flame retardants, and pot life extenders may also be included in the first curable clear composition.

[0033] Organic solvents can be used to adjust the viscosity of the reactive mixture used to produce the first clearcoat layer 104. Such organic solvents can include ether acetates, propylene glycol monomethyl ether acetate, ketones, benzene derivatives, and mixtures thereof. The amount of solvent can be selected to facilitate proper mixing and casting of the curable polyurethane composition. The organic solvents used are generally volatile so that they can be removed prior to or simultaneously with the curing of the first clearcoat layer 104. Such evaporation can be facilitated by heat, vacuum, or both.

[0034] When the aforementioned reactive components are mixed and heated sufficiently, they polymerize and become a crosslinked network. The crosslink density of a polyurethane is calculated by dividing the weight of reactive components having a functionality of 3 or more by the total weight of the polyurethane and multiplying by 100. High crosslink densities (e.g., greater than 30 percent) are generally associated with rigid polyurethane materials. However, the use of primary aliphatic polyisocyanates can enable polyurethanes that are both flexible and have high crosslink densities. Useful crosslink densities can be 25% to 100%, 30% to 100%, or in some embodiments, less than, equal to, or greater than 25%, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% or 100%.

[0035] The final thickness of the first clear coat layer 104 can vary depending on the end application needs. Typically, the thickness of the first clear coat layer 104 is between 2 micrometers and 25 micrometers, between 2 micrometers and 20 micrometers, between 2 micrometers and 15 micrometers, or in some embodiments, less than, equal to, or greater than 2 micrometers, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 17, 20, 22, or 25 micrometers.

[0036] The second clear coat layer 106 extends along and is in flush contact with the bottom surface 110 of the first clear coat layer 104. The second clear coat layer 106 is produced by at least partially curing a second polyurethane composition. The use of a second polyurethane composition that is only partially crosslinked (i.e., partially cured) can be advantageous when the second clear coat layer 106 is used as a primer to enhance adhesion with the first clear coat layer 104. In some embodiments, secondary bonds (e.g., hydrogen bonds) occur at the interface between the first and second polyurethane clear coat layers, resulting in increased interlayer adhesion. In some embodiments, the first clear coat layer 104 can also be only partially cured when the two layers are brought together, as described below.

[0037] The second polyurethane composition can have similar properties to the first polyurethane composition described above, but differs from the first polyurethane composition in that it does not contain a polyol containing styrene repeat units and hydroxyl-containing (meth)acrylate repeat units.

[0038] In some embodiments, the second polyurethane composition is an aqueous polyurethane dispersion.Preferred aqueous polyurethane dispersions include aliphatic polycarbonate polyurethane dispersions.The dispersion can use a solvent system that includes water and one or more cosolvents.Certain cosolvents, such as diethylene glycol monomethyl ether, can be useful for improving coating quality by reducing the volatility of the dispersion.

[0039] The polyurethane dispersion can include any of a number of suitable surfactants, such as anionic surfactants. Anionic surfactants include, for example, sulfates such as sodium dodecyl sulfate, ammonium dodecyl sulfate, and sodium lauryl ether sulfate, and sulfosuccinates such as dioctyl sodium sulfosuccinate and disodium lauryl sulfosuccinate. In the above-mentioned water-based polyurethanes, these surfactants can be used in combination with co-dispersants. Co-dispersants include amino alcohols. Amino alcohols such as 2-amino-2-methyl-1-propanol can help neutralize acid-functional resins and are suitable for use in water-based coatings.

[0040] The second polyurethane composition can include any suitable crosslinking agent, such as a polyfunctional aziridine liquid crosslinking agent. The amount of crosslinking agent is not critical and can be selected to provide the desired degree of crosslinking. The amount of crosslinking agent can be less than, equal to, or greater than 0.5% to 5%, 0.5% to 4%, 0.5% to 3%, or in some embodiments, 0.5%, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.5, 1.7, 2, 2.2, 2.5, 2.7, 3, 3.2, 3.5, 3.7, 4, 4.2, 4.5, 4.7, or 5% by weight, based on the total weight of the second polyurethane composition.

[0041] Although not critical, other additives such as UV absorbers and stabilizers can also be included in either or both of the first and second polyurethane compositions.Stabilizers can include hindered amine light stabilizers that eliminate free radicals generated by photo-oxidation of polymers.Advantageously, these additives can help minimize defects caused by cracks and gloss loss in clear coat layers.

[0042] In a preferred embodiment, the aqueous polyurethane dispersion is a polycarbonate polyurethane having a solids content of 30% to 40% by weight and a total solvent content of 5% to 15% by weight.

[0043] The second clear coat layer 106 has a chemical composition that allows it to adhere permanently to the first clear coat layer 104. Preferably, the first and second clear coat layers 104, 106 do not peel off from each other during the life of the surfacing film 100, even under harsh environments. Advantageously, the provided surfacing film 100 uses a second clear coat layer 106 that can adhere strongly to the prefabricated first clear coat layer 104 obtained by curing a reactive mixture as described above.

[0044] The thickness of the second clear coat layer 106 need not be particularly limited. In some embodiments, the thickness can be similar to the thickness of the first clear coat layer 104. Typically, the thickness of the second clear coat layer 106 when cured is between 2 micrometers and 30 micrometers, between 2 micrometers and 25 micrometers, between 2 micrometers and 15 micrometers, or in some embodiments, less than, equal to, or greater than 2 micrometers, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 17, 20, 22, 25, 27, or 30 micrometers.

[0045] Referring again to FIG. 1, the composite clearcoat layer 102 is disposed on a bulk layer 112 that extends across and is in continuous contact with the bottom surface of the second clearcoat layer 106 .

[0046] In a preferred embodiment, the bulk layer 112 is composed of a thermoplastic polyurethane. However, it is also possible for the bulk layer 112 to be made of polyesters and / or polyolefins, such as polypropylene, polyethylene and blends of polyethylene and polypropylene, ethylene modified copolymers, such as ethylene-vinyl acetate, ethylene-(meth)acrylic acid, ethylene-methacrylate, or blends thereof. Bulk layer compositions useful for surface films protecting the exterior surfaces of automobiles include ionomers of olefin / vinyl carboxylate copolymers, such as ethylene-acrylic acid and ethylene-methacrylic acid copolymers, in combination with various metal cations, including lithium, sodium, potassium, zinc, aluminum, and calcium cations. Suitable commercially available ionomer resins include materials available under the trade name SURLYN from EI DuPont de Nemours & Co. (Wilmington, Del.).

[0047] In a preferred embodiment, bulk layer 112 is an aliphatic thermoplastic polyurethane, which can provide excellent optical properties, high flexibility, good heat and UV resistance, and good chip resistance.

[0048] The thickness of the bulk layer 112 is not particularly limited. It is preferably thin enough to allow the entire surface film 100 to stretch as necessary to conform to a substrate having a curved or irregularly shaped three-dimensional contour, but thick enough to protect the substrate against abrasion and impacts encountered during use. The thickness of the bulk layer 112 can be 50 micrometers to 500 micrometers, 50 micrometers to 500 micrometers, 50 micrometers to 350 micrometers, or in some embodiments, less than, equal to, or greater than 50 micrometers, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 270, 300, 325, 350, 375, 400, 450, or 500 micrometers.

[0049] The adhesive layer 114 extends across and is in direct contact with the major surface of the bulk layer 112 facing away from the first and second clearcoat layers 104, 106. The adhesive layer 114 is a pressure sensitive adhesive and is typically tacky at ambient conditions. Suitable pressure sensitive adhesives may be polyacrylate based, synthetic and natural rubber based, polybutadiene and copolymer based, or polyisoprene and copolymer based. Optionally, silicone based adhesives such as polydimethylsiloxane and polymethylphenylsiloxane may also be used.

[0050] Particularly preferred pressure-sensitive adhesives include polyacrylate adhesives, which can show advantageous properties such as high transparency, UV stability and aging resistance.Polyacrylate adhesives that can be used for surface film applications are described in, for example, U.S. Patent No. 4,418,120 (Kealy et al.), U.S. Patent No. RE24,906 (Ulrich), U.S. Patent No. 4,619,867 (Charbonneau et al.), U.S. Patent No. 4,835,217 (Haskett et al.) and International Patent Publication WO87 / 00189 (Bonk et al.).

[0051] Preferably, the polyacrylate pressure sensitive adhesive comprises a crosslinkable copolymer of C4-C12 alkyl acrylate and acrylic acid. The adhesive can be used with or without a crosslinker. Useful crosslinking reactions include chemical and ionic crosslinking. Chemical crosslinkers can include polyaziridines and / or bisamides, and ionic crosslinkers can include metal ions of aluminum, zinc, zirconium, or mixtures thereof. Mixtures of chemical and ionic crosslinkers can also be used. In some embodiments, the polyacrylate pressure sensitive adhesive comprises a tackifier such as a rosin ester. The adhesives useful in the present invention may also contain additives such as ground glass, titanium dioxide, silica, glass beads, waxes, tackifiers, low molecular weight thermoplastics, oligomeric species, plasticizers, pigments, metal flakes, and metal powders, so long as they are provided in amounts that do not unduly degrade the quality of the bond of the adhesive to the surface.

[0052] As an alternative to a pressure sensitive adhesive, adhesive layer 114 may be a hot melt adhesive that is not tacky at room temperature but becomes tacky when heated. Such adhesives include acrylic, ethylene vinyl acetate, and polyurethane materials.

[0053] Generally, adhesive layer 114 can have a thickness of less than, equal to, or greater than 15 micrometers to 60 micrometers, 15 micrometers to 50 micrometers, 15 micrometers to 45 micrometers, or in some embodiments, 15 micrometers, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55, or 60 micrometers.

[0054] In certain applications, such as applying the surfacing film 200 to an automotive exterior, it may be desirable for the adhesive to be at least initially repositionable so that the sheet can be adjusted to fit a desired location before a permanent bond is formed. Such repositionability can be achieved, for example, by providing a layer of microscopic glass bubbles on the adhesive surface, as disclosed in U.S. Patent No. 3,331,729 (Danielson et al.).

[0055] 2 illustrates a surfacing film 200 according to an alternative embodiment. Similar to surfacing film 100, surfacing film 200 includes a composite clear coat layer 202 including a first clear coat layer 204 and a second clear coat layer 206, along with an adhesive layer 214 on the opposing major surface of surfacing film 200.

[0056] However, unlike the previous embodiment, the composite clear coat layer 202 is disposed on the composite bulk layer. The composite bulk layer shown has a two-layer structure including a transparent bulk layer 213 and a colored bulk layer 212. Optionally, both the transparent bulk layer 213 and the colored bulk layer 212 can be manufactured using the same matrix polymer, such as thermoplastic polyurethane, polyester, polyolefin, or any of their blends, as described above. In a preferred embodiment, the colored bulk layer 212 contains a sufficient amount of colorant to fill the layer with color, while the transparent bulk layer 213 is essentially free of colorant. Useful colorants are not limited and can include any dye or pigment known in the art, including metal flakes and pearlescent pigments. The amount of colorant in the colored bulk layer 212 is also not limited and may be sufficient to make the layer opaque. In an alternative embodiment, the transparent bulk layer 213 is replaced with a semi-transparent colored layer, such as a lightly filled pearlescent pigment layer. In this case, the pigmented bulk layer 212 may be, for example, a white pigmented base layer having a pigment loading substantially higher than the pigment loading of the pearlescent pigment layer.

[0057] According to yet another embodiment, although not explicitly shown here, the colored bulk layer 212 may itself include two or more constituent sublayers. For example, the colored bulk layer 212 may include a base sublayer below the colored sublayer, both of which extend below the transparent bulk layer 213. Based on the pigment selection and loading, the colored sublayer may be translucent and the base sublayer may be substantially opaque or reflective. As a further example, the base sublayer may contain light absorbing or reflective metal flakes and the colored sublayer may be translucent and contain pearlescent pigments.

[0058] Advantageously, the use of such multiple bulk layers allows the surfacing film to exhibit an enhanced visual perception of depth to the viewer, thereby providing improved aesthetics. This depth perception is provided by the transparent bulk layer 213, which effectively extends the visually apparent depth of the composite clear coat layer 202, while the colored bulk layer 212 preserves the desired background of the surfacing film 200. Because the highly crosslinked nature of the first clear coat layer 204 tends to have a strong stiffening effect, this configuration can provide this enhanced depth perception without adversely affecting the handling properties of the surfacing film 200 overall.

[0059] In those embodiments using a dual layer bulk layer, the relative proportions between the transparent bulk layer 213 and the colored bulk layer 212 can be varied according to the desired visual effect. The transparent bulk layer 213 can have a thickness between 25 micrometers and 125 micrometers, or in some embodiments, a thickness that is less than, equal to, or greater than 25 micrometers, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 105, 110, 115, 120, or 125 micrometers. The colored bulk layer 212 can have a thickness of from 25 micrometers to 375 micrometers, or in some embodiments can have a thickness that is less than, equal to, or greater than 25 micrometers, 30, 35, 40, 45, 50, 55, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, or 375 micrometers.

[0060] Manufacturing Process Significant technical advantages offered by the provided surfacing films and associated processes stem from improvements in throughput, web handling, and quality control in manufacturing these films.

[0061] An exemplary process for manufacturing the provided surface films is provided in the block diagram of FIG.

[0062] At block 250, a first curable polyurethane clearcoat composition is placed on a release liner or other release surface. This clearcoat composition is a liquid and can be coated using any known technique. Suitable techniques include, for example, coating or extrusion onto a release liner. Coating and extrusion of the disclosed curable clearcoat composition can be performed using either batch or continuous techniques.

[0063] In an exemplary extrusion process, the components of the first curable polyurethane clearcoat composition are first mixed into two separate parts to prevent premature reaction. One part can be prepared by first mixing the polyol component, a suitable solvent (if necessary), and any optional additives. The other part contains the isocyanate component along with any solvent or optional additives. The first and second parts are then mixed in appropriate amounts to obtain the desired NCO:OH ratio. In these embodiments, the NCO:OH ratio can be selected to be between 0.75 and 1.25.

[0064] Once mixed, the composition can be coated onto a release surface, such as a polyester release liner. The coating can be produced using conventional equipment, such as a knife coater, roll coater, reverse roll coater, notched bar coater, curtain coater, rotogravure coater, or rotary printer. The coating can be hand-spread or automated, and may be carried out according to either a batch or continuous process. The viscosity of the composition can be adjusted as necessary to suit the type of coater used.

[0065] The first curable polyurethane clearcoat composition is then cured, as provided at block 252. This can be accomplished by subjecting the clearcoat composition to heat and / or vacuum to remove the organic solvent and any other volatile components, heat activate the curing reaction between the polyol and the isocyanate, and partially cure the clearcoat composition. In some embodiments, the first curable polyurethane clearcoat composition is 45%-55% cured, 40%-60% cured, 30%-70% cured, or in some embodiments, less than, equal to, or greater than 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70% cured.

[0066] It has been found that partial curing of a first curable clearcoat composition improves adhesion of the second clearcoat layer to the first clearcoat layer, especially when a second curable polyurethane clearcoat composition is placed on the partially cured first curable clearcoat composition and both layers are cured together. In contrast, it has been observed that fully curing the first curable clearcoat composition reduces adhesion of the first and second clearcoat layers to each other.

[0067] An oven can be used to first evaporate the solvent and partially cure the composition. Generally, the drying / curing steps are performed in air. If continuous processes are used, these processes can operate on a moving web. In an exemplary continuous process, a wet coating 0.0076 centimeters (0.003 inches) thick can have a solids content of about 45% and can be dried and cured using a temperature profile with a dwell time of 2 minutes at 80°C, followed by a dwell time of 10 minutes at 125°C.

[0068] Generally, the clearcoat composition is preferably dried and / or cured at a predetermined temperature of from 25°C to 150°C, or in some embodiments at a predetermined temperature that is less than, equal to, or greater than 25°C, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or 150°C. The residence time at a given temperature is highly dependent on the temperature, but can be from 5 seconds to 180 seconds, from 5 seconds to 150 seconds, from 5 seconds to 120 seconds, or in some embodiments can be less than, equal to, or greater than 5 seconds, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, or 180 seconds. The clearcoat composition is preferably subjected to a residence time and temperature or temperature range that balances solvent removal and curing effectiveness with overall throughput and energy efficiency.

[0069] At block 254, a second curable polyurethane clearcoat composition is disposed over the partially cured first clearcoat layer, which is still supported on the release liner. The second curable polyurethane clearcoat composition can be an aqueous polyurethane dispersion or emulsion. Commercially available polyurethane dispersions and emulsions include, for example, those manufactured by Alberdingk Boley, Inc., Greensboro, NC.

[0070] Any known method can be used to dispose the second curable polyurethane clearcoat composition over the underlayer, including any of those described above for coating the first curable polyurethane clearcoat composition.

[0071] At block 256, the second curable polyurethane clearcoat composition is cured to provide a second clearcoat layer. Typically, heat is again applied to evaporate water and / or any other volatile species, and then the first and second clearcoat layers are cured. The oven temperature profile may be similar to that described above for partially curing the first curable polyurethane clearcoat composition. However, the degree of cure need not be limited to this second cure cycle, so it may be advantageous to use a higher temperature or increase the duration of the curing step if the temperature does not increase significantly.

[0072] In some embodiments, the first and second clear coat layers can continue to cool and cure after the heating step and before any further coating or lamination steps. This can be accomplished by aging the composite clear coat layer at ambient conditions. Aging is performed for at least 1 week, at least 2 weeks, at least 3 weeks, or at least 4 weeks to allow the first and second clear coat layers to reach a generally stable and consistent degree of crosslinking.

[0073] Block 258 indicates the next step, in which one or more thermoplastic polyurethane bulk layers are disposed on the exposed major surface of the second clearcoat layer. When more than one thermoplastic polyurethane bulk layer is present, as in surfacing film 200 of Figure 2, the individual layers may be produced simultaneously (e.g., by coextrusion) or may be produced at different times and later combined.

[0074] By this time, both the first and second clearcoat layers are functionally cured. In some embodiments, the thermoplastic polyurethane layer can be melt processed and extruded from the melt directly onto the composite clearcoat layer. In an alternative embodiment, the thermoplastic polyurethane layer can be melt processed and formed separately into a uniform sheet and then subsequently thermally laminated to the composite clearcoat layer.

[0075] As shown in block 260, a pressure-sensitive adhesive layer of the above composition can then be placed on the thermoplastic polyurethane layer. As with the bulk layer, the adhesive layer can be coated directly onto the remaining layer of the surface film, or can be formed into an adhesive film and then laminated to the bulk layer in a subsequent step. In the latter case, a sacrificial release liner is typically placed in contact with the adhesive layer to facilitate handling and storage of the web. In other embodiments, an adhesive other than a pressure-sensitive adhesive can be used in place of the pressure-sensitive adhesive layer in block 260.

[0076] Optionally, the steps of blocks 258 and 260 can be performed in reverse order. For example, the pressure sensitive adhesive and polyurethane bulk layer can be provided together on a release liner, and then a clearcoat layer can be laminated together to the polyurethane bulk layer / adhesive / liner to provide a finished surfacing film.

[0077] An important advantage of placing the bulk layer on the composite clear coat layer after the composite clear coat layer is essentially fully cured is the reduction or even elimination of impurities in the polyurethane bulk layer and / or the pressure-sensitive adhesive. This advantage arises from essentially excluding all solvents and other volatile compounds from the composite clear coat layer before the composite clear coat layer is placed in contact with the remaining layers. In contrast, conventional methods place an uncured clear coat composition on the bulk layer. As a result, solvent from the uncured clear coat composition may penetrate into the bulk layer. This, in turn, may cause significant softening of the bulk layer, and impurities in the bulk layer, such as waxes and anti-stick agents, may migrate into the adjacent pressure-sensitive adhesive layer, reducing bonding performance.

[0078] Unexpectedly, reducing / eliminating the migration of small molecules into the bulk layer also had the effect of providing a more stable stiffness to the surface film. Since the bulk layer is made from thermoplastic polyurethane, it tends to harden as a result of the isocyanate-based crosslinker migrating from the first clear coat layer through the second clear coat layer along with the solvent and other additives into the bulk layer. This can result in minor crosslinking of the bulk layer over a period of 2-3 months. As this occurs during storage, it results in the final product having inconsistent film stiffness, which is undesirable. This phenomenon can be observed by attempting to dissolve the thermoplastic bulk layer in a suitable solvent, which, if this layer is partially crosslinked, does not dissolve completely.

[0079] Yet another advantage of the aforementioned process is the possibility of producing the layers in the surface film in stages. The constituent layers can be produced continuously in successive stages on an inexpensive release liner. If the composite clear coat layer is produced first, it is possible to optimize the extrusion of the bulk layer onto the inexpensive release liner, and then replace the release liner with the composite clear coat layer and fuse the layers together. A similar process can be used to apply the adhesive layer to the bulk layer. This improvement can significantly improve the product yield and minimize the waste of polyurethane film.

[0080] Uses and characteristics The surface films provided can be useful in paint protection and paint replacement applications. These films can be applied to any of a wide variety of substrates. Such substrates can be flat or curved. When it is desired to adhere these surface films to such curved surfaces, the article preferably has sufficient flexibility to conform to the surface of the substrate without delaminating or wrinkling at the edges.

[0081] Common substrates suitable for protection include, for example, bumper fascias, pillar posts, rocker panels, wheel covers, headlights, door panels, trunk and hood lids, mirror housings, dashboards, floor mats, and door sills. In an exemplary process of application, the surface film can be attached to a suitable substrate by simultaneously peeling the release liner from the adhesive layer while applying the film onto the substrate in a single continuous motion.

[0082] In some embodiments, the surface films provided are applied to the exterior surfaces of automobiles, trucks, motorcycles, trains, airplanes, rotorcraft, watercraft, and snowmobiles. In alternative embodiments, the surface films can be applied to the surfaces of structures other than vehicles, such as fixtures, buildings, and architectural surfaces. The applications of these films can be either indoor or outdoor in nature. The surface films provided are particularly advantageous outdoors, not only because of their low surface energy and easy cleaning properties, but also because they exhibit excellent weather resistance, chemical resistance, and abrasion resistance while maintaining high flexibility.

[0083] In some embodiments, the surface film has an exposed top surface. Advantageously, the first clear coat layer 104 provides a combination of desirable optical and mechanical properties that make it particularly suitable as an outermost layer in protective film applications.

[0084] The optical properties of the clear coat layer or surface film can be characterized by its measured light transmission and haze value. In general, it is desirable to have as low a haze as possible for clear coat applications. The transmission and haze value of the clear coat layer sample can be obtained, for example, using a Haze-Gard Plus instrument available from BYK Gardner USA, Columbia, MD. The cured clear coat layer or surface film preferably exhibits a haze value of less than 6%, less than 5%, less than 4%, less than 3.5%, or less than 3%, as measured according to the haze test as described in U.S. Pat. No. 10,711,156 (Ho et al.). The cured first clear coat layer 104 also exhibits a stain-resistant clear coat surface. EXAMPLES

[0085] Objects and advantages of the present disclosure are further illustrated by the following non-limiting examples, in which the specific materials and amounts thereof recited, as well as other conditions and details, should not be construed to unduly limit the disclosure. Unless otherwise indicated, all parts, percentages, ratios, etc. in the examples and elsewhere in this specification are by weight. [Table 1]

[0086] Test Method: Contamination The adhesive side of the specimen was adhered to a standard RK8014 clearcoat white painted panel available from ACT Test Panels Technologies of Hillsdale, MI, United States. A 1-inch diameter stain was placed on the specimen and aged for 24 hours at 75°F. After 24 hours, the specimen was washed with paint naphtha (VM&P Naphtha, Ashland Chemical Co., Covingto, KY. United States). The yellowness (Δb) and total color change (ΔE) were measured using a colorimeter before and after staining. Testing was performed using a stain prepared by mixing 50% by volume of AC-20 non-emulsified asphalt cement (Marathon Petroleum Company, Findlay, OH. United States) in unleaded gasoline. The specimen was immersed in the stain for 10 seconds and then hung in a fume hood chamber for 15 minutes to allow the stain to evaporate. The specimen was washed with paint naphtha. When the test was performed, the odor was as described and a text comment was recorded as to whether or not the odor was detected.

[0087] Example 1 (EX1) A first reactive polyurethane clear coating solution was prepared by mixing 6.8 grams of CAPA-2054, 27.2 grams of J587-AC, 0.43 grams of T-405, 0.35 grams of T-292, 0.43 grams of T-479, 19.75 grams of PMA, 23.0 grams of BA, 19.84 grams of xylene, 2.20 grams of C-381, 11.72 grams of N3390, and 0.9 grams of a 97.5:2.5 ratio mixture of AA and T-12. The mixture of clear coat solution was thoroughly stirred for 15 minutes, and the solution was coated onto a melamine acrylic primed polyester release carrier web by an 11 inch wide die coater. The solution flow rate was controlled at 45 grams / min, and the line speed was 12 feet / min. The reactive polyurethane clearcoat was cured in an air oven at 240° F. The resulting dry thickness of the first clearcoat was about 8 micrometers.

[0088] A second reactive polyurethane clear coating solution was prepared by mixing 83.78 grams of U9190, 0.35 grams of T-123, 0.03 grams of AMP-95, 0.19 grams of GR-7M, 8.47 grams of BC, 1.08 grams of T-405, 0.45 grams of T-292, 14.0 grams of deionized water, and 2.0 grams of CX-100. The solution mixture was mixed thoroughly for about 15 minutes. The second reactive polyurethane clear coat solution mixture was then coated onto the first reactive polyurethane clear coat at a flow rate of 40 grams / minute and 12 feet / minute. The dual layer clear coat was cured in an air oven while progressing through three temperature zones: 200°F, 250°F, and 275°F. The oven residence time in each zone was about 38 seconds. The dry thickness of the second clearcoat was about 12 micrometers.

[0089] The dual layer clear coat was then thermally laminated to a surface protective urethane film (obtained from 3M Company, St. Paul, MN. United States), which included a layer of urethane film, an adhesive (isoacetyl acetate / acrylic acetate / vinyl acetate), and a polyester release liner. The hot can temperature was set at 235°F, the nip roll pressure was set at 40 psi, and the line speed was 15 feet / min. The polyester carrier web on the first reactive polyurethane clear coat surface was removed after 24 hours. The dual layer clear coat-based paint protection film was aged at room temperature for 4 weeks before testing. Staining tests were performed and the results are shown in Table 2.

[0090] Example 2 (EX2) A first reactive polyurethane clear coating solution was prepared by mixing 4.0 grams of F55-112, 4.0 grams of F55-225, 4.0 grams of CAPA-3031, 15.0 grams of S17-1608, 1.0 grams of T-405, 0.5 grams of T-292, 13.3 grams of PMA, 23.3 grams of BA, 80.5 grams of MIBK, 10.0 grams of xylene, 2.50 grams of C-381, 18.73 grams of N3390, and 1.9 grams of a 97.5:2.5 ratio mixture of AA and T-12. The clear coat solution mixture was thoroughly stirred for 15 minutes and the solution was coated onto a melamine acrylic primed polyester release carrier web by an 11 inch wide die coater. The solution flow rate was controlled at 35 grams / minute and the line speed was 25 feet / minute. The reactive polyurethane clearcoat was cured in an air oven at 290°F for a total residence time of about 84 seconds. The resulting first clearcoat thickness was about 4.0 micrometers.

[0091] A second reactive polyurethane clear coating solution was prepared by mixing 89.30 grams of U933, 0.35 grams of T-123, 0.05 grams of AMP-95, 0.20 grams of GR-7M, 8.5 grams of BC, 1.16 grams of N3039, 38.0 grams of deionized water, and 1.78 grams of CX-100. The solution mixture was mixed thoroughly for about 15 minutes. The second reactive polyurethane clear coat solution mixture was then coated onto the first reactive polyurethane clear coat at a flow rate of 40 grams / minute and 20 feet / minute. The clear coat was cured in an air oven while progressing through two temperature zones at 225°F and 290°F. The oven residence time in each zone was about 54 seconds. The dry thickness of the second clear coat was about 6.13 micrometers.

[0092] The dual layer clearcoat was then thermally laminated to a surface protective urethane film (obtained from 3M Company) that included a layer of urethane film, a layer of adhesive (isoacetyl acetate / acrylic acetate / vinyl acetate), and a polyester release liner. The hot can temperature was set at 235°F, the nip roll pressure was set at 40 psi, and the line speed was 15 feet / minute. The polyester carrier web on the first reactive polyurethane clearcoat surface was removed after 24 hours. The dual layer clearcoat-based paint protection film was aged at room temperature for 4 weeks before testing. Staining tests were performed and the results are shown in Table 2.

[0093] Comparative example 1 (CE1) The solvent-based clearcoat (assembled as described in EX1 or EX2) was coated directly onto a standard urethane film (obtained from 3M Company, St. Paul, MN. United States), which contained a 125 micrometer layer of urethane film, a 35 micrometer layer of standard adhesive (isoacetyl acetate / acrylic acetate / vinyl acetate), and a polyester release liner, and was cured in an air oven at 146.11°C (295°F).

[0094] Comparative Example 2 (CE2) Staining tests were performed on ULTIMATE PLUS film (obtained from XPEL, Inc., San Antonio, TX, United States), and the results are shown in Table 2.

[0095] Comparative Example 3 (CE3) Dye tests were performed on Extreme film (obtained from XPEL, Inc., San Antonio, TX, United States), and the results are shown in Table 2.

[0096] Comparative Example 4 (CE4) Stain testing was performed on PPF Clear film (obtained from SUNTEK, a subsidiary of Eastman Performance Film, Martinsville, VA, United States), and the results are shown in Table 2. [Table 2]

[0097] All documents, patent documents or patent applications cited in the above patent application for letters patent are incorporated herein by reference in their entirety in a consistent manner. In the event of any inconsistency or discrepancy between any of the incorporated references and this application, the information in the foregoing description shall prevail. The foregoing description is intended to enable a person skilled in the art to practice the disclosure as set forth in the claims, and should not be construed as limiting the scope of the present disclosure, which is defined by the claims and all equivalents thereof.

Claims

1. Multiple layers in the following order: a first clearcoat layer comprising a crosslinked polyurethane that is the reaction product of a reactive mixture comprising an isocyanate and a polyol containing styrene repeat units and hydroxyl-containing (meth)acrylate repeat units; a bulk layer comprising a thermoplastic polyurethane; an adhesive layer; Including, surface film.

2. 10. The surfacing film of claim 1, further comprising a second clear coat layer comprised of an at least partially crosslinked polymer.

3. 3. The surfacing film of claim 2, wherein the second clear coat layer is comprised of an at least partially crosslinked polyurethane.

4. The surfacing film of claim 3 , wherein the polyurethane of the second clear coat layer is a water-based polyurethane.

5. 10. The surfacing film of claim 1, wherein the isocyanate is an aliphatic isocyanate.

6. The surfacing film of any one of claims 1 to 5, wherein the bulk layer comprises an aliphatic thermoplastic polyurethane.

7. 7. The surfacing film of claim 6, wherein the bulk layer further comprises a pigmented thermoplastic polyurethane layer and a transparent or translucent thermoplastic polyurethane layer disposed thereon.

8. 8. The surfacing film of claim 7, wherein the pigmented thermoplastic polyurethane layer comprises a pigment sublayer that is translucent and a base sublayer that is substantially opaque.

9. 1. A process for producing a surface film, comprising: disposing a first curable polyurethane clearcoat composition onto a first release liner, the first curable polyurethane clearcoat composition comprising a copolymer of styrene and a hydroxyl-containing (meth)acrylate; only partially curing the first curable polyurethane clearcoat composition to provide a first clearcoat layer; disposing a second curable polyurethane clearcoat composition over the first clearcoat layer; at least partially curing the second curable polyurethane clearcoat composition to provide a second clearcoat layer over the first clearcoat layer; disposing a thermoplastic polyurethane layer over the second clear coat layer; disposing an adhesive layer on the thermoplastic polyurethane layer; The process includes:

10. the first curable polyurethane clearcoat composition comprising: Isocyanate, a polyol containing styrene repeat units and hydroxyl-containing (meth)acrylate repeat units; 10. The process of claim 9, comprising:

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